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US7326759B2 - Compositions for solid freeform fabrication - Google Patents

Compositions for solid freeform fabrication Download PDF

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Publication number
US7326759B2
US7326759B2 US10/817,047 US81704704A US7326759B2 US 7326759 B2 US7326759 B2 US 7326759B2 US 81704704 A US81704704 A US 81704704A US 7326759 B2 US7326759 B2 US 7326759B2
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Prior art keywords
composition
component
combinations
acid
binder
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US10/817,047
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US20050222354A1 (en
Inventor
Isaac Farr
Terry M. Lambright
Vladek Kasperchik
Christopher Oriakhi
Jurgen Engelbrecht
Ade Akinmade
David A Neel
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Hewlett Packard Development Co LP
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Hewlett Packard Development Co LP
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Assigned to HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P. reassignment HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KASPERCHIK, VLADEK P., ORIAKHI, CHRISTOPHER, FARR, ISAAC, LAMBRIGHT, TERRY M., NEEL, DAVID A., AKINMADE, ADE, ENGELBRECHT, JURGEN
Priority to US10/817,047 priority Critical patent/US7326759B2/en
Priority to TW094106642A priority patent/TW200533726A/en
Priority to EP05734054A priority patent/EP1747498B1/en
Priority to AT05734054T priority patent/ATE432961T1/en
Priority to JP2007506254A priority patent/JP4695134B2/en
Priority to CN200580010249XA priority patent/CN101098927B/en
Priority to PCT/US2005/009691 priority patent/WO2005098538A2/en
Priority to DE602005014767T priority patent/DE602005014767D1/en
Assigned to FIRST SCIENTIFIC DENTAL GMBH, HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P. reassignment FIRST SCIENTIFIC DENTAL GMBH RECORD TO ADD OMITTED RECEIVING PARTY, PREVIOUSLY RECORDED AT REEL 015187 FRAME 0534. Assignors: KASPERCHIK, VLADEK P., ORIAKHI, CHRISTOPHER, FARR, ISAAC, LAMBRIGHT, TERRY M., NEEL, DAVID A., AKINMADE, ADE, ENGLEBRECHT, JURGEN
Publication of US20050222354A1 publication Critical patent/US20050222354A1/en
Priority to IL177810A priority patent/IL177810A0/en
Publication of US7326759B2 publication Critical patent/US7326759B2/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0037—Production of three-dimensional images
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters

Definitions

  • Solid freeform fabrication SFF
  • LM layer manufacturing
  • SFF Solid freeform fabrication
  • CAD Computer Aided Design
  • SFF technology enables direct translation of the CAD image data into a three-dimensional object.
  • SFF technology can be used in applications such as verifying CAD database, evaluating design feasibility, testing part functionality, assessing aesthetics, checking ergonomics of design, aiding in tool and fixture design, creating conceptual models and sales/marketing tools, generating patterns for investment casting, reducing or eliminating engineering changes in production, and providing small production runs.
  • One SFF technique involves adding or depositing a build composition to form predetermined areas of a layer essentially point-by-point. These predetermined areas together constitute a thin section of a three-dimensional object as defined by a CAD geometry. Successive layers are then deposited in a predetermined sequence with a layer being affixed to its adjacent layers forming an integral three dimensional, multi-layer object.
  • a powder/binder SFF system an individual layer is printed by first spreading a thin layer of the powder and then dispensing the binder to adhere the powder together in selected regions to create the desired layer pattern. This process is repeated until all the layers have been printed.
  • the binder joins powder together within a layer and between layers. After printing is complete, the unbound powder is removed, leaving a three-dimensional object with the desired geometry.
  • compositions include compositions.
  • One exemplary composition of this disclosure includes a basic component, an acidic component, at least one acrylate component, oxidizing agent, reducing agent, and a binder.
  • the binder includes a viscosity modifier and a surface tension modifier.
  • the binder is capable of stimulating a reaction between the basic component and the acidic component.
  • a portion of the binder is capable of undergoing a polymerization reaction between at least one acrylate component, the oxidizing agent, and the reducing agent. The polymerization reaction being initiated by the redox reaction between the oxidizing agent and the reducing agent.
  • FIG. 1 illustrates an embodiment of a solid freeform fabrication (SFF) system.
  • FIG. 2 illustrates a flow diagram of a representative embodiment for forming a three-dimensional object using the SFF system described in FIG. 1
  • compositions that can be used in solid freeform fabrication (SFF) systems are provided.
  • the embodiments relate to the use of the compositions in the manufacture of three-dimensional objects.
  • the term three-dimensional object refers to objects that are sufficiently rigid to maintain a fixed volume and shape to an extent, which is appropriate for the specific use.
  • Embodiments of the composition can include components such as, but not limited to, a basic component, an acidic component, at least one acrylate component (e.g., mono-, di-, tri-, tetra-acrylate compounds), an oxidizing agent, a reducing agent, a light sensitive initiator, and combinations thereof.
  • a basic component an acidic component
  • at least one acrylate component e.g., mono-, di-, tri-, tetra-acrylate compounds
  • an oxidizing agent e.g., mono-, di-, tri-, tetra-acrylate compounds
  • one embodiment of the composition includes, but is not limited to, the basic component, the acidic component, one or more acrylate components, the oxidizing agent, and the reducing agent.
  • Another embodiment of the composition includes, but is not limited to, the basic component, the acidic component, one or more acrylate components, and the light sensitive initiator.
  • Still another embodiment of the composition includes, but is not limited to, the basic component, the acidic component, one or more acrylate components, the oxidizing agent, the reducing agent, and the light sensitive initiator.
  • composition can include additional components such as, but not limited to, retardants, wetting agents, viscosity modifiers, surface tension modifiers, fibers, colorants, dispersants, antioxidants, organic and inorganic fillers, solvents, and combinations thereof.
  • retardants such as, but not limited to, retardants, wetting agents, viscosity modifiers, surface tension modifiers, fibers, colorants, dispersants, antioxidants, organic and inorganic fillers, solvents, and combinations thereof.
  • the components of the composition can be included in a powder and/or a binder.
  • the ratio of binder to powder can be from about 0.05:1 to 0.6:1, and from about 0.1:1 to 0.4:1.
  • the ratio of binder to powder depends upon many variables such as, but not limited to, the components, the concentration of each component, and the percentage of each component in the powder; the components, the concentration of each component, and the percentage of each component in the binder; and combinations thereof.
  • the powder includes, but is not limited to, the basic component, the acidic component, a polyacrylate component, and the oxidizing agent
  • the binder includes, but is not limited to, a solvent (e.g., a polar solvent such as water), an acrylate component (e.g., monomeric acrylate), and the reducing agent.
  • Another embodiment of the powder includes, but is not limited to, the basic component, a polyacrylate component, and the oxidizing agent while the binder includes, but is not limited to, the solvent, the acidic component, the acrylate component, and the reducing agent.
  • the powder includes, but is not limited to, the basic component, an acidic component, a polyacrylate component, and the oxidizing agent, while the binder includes, but is not limited to, the solvent, another acidic component, the acrylate component, and the reducing agent.
  • the powder includes, but is not limited to, the basic component, the acidic component and a polyacrylate component, while the binder includes, but is not limited to, the solvent, the acrylate component, and the light sensitive initiator.
  • the powder includes, but is not limited to, the basic component and a polyacrylate component
  • the binder includes, but is not limited to, the solvent, the acidic component, the acrylate component, and the light sensitive initiator.
  • the powder includes, but is not limited to, the basic component, an acidic component, and a polyacrylate component
  • the binder includes, but is not limited to, the solvent, another acidic component, the acrylate component, and the light sensitive initiator.
  • the powder includes, but is not limited to, the basic component, the acidic component, a polyacrylate component, and the oxidizing agent, while the binder includes, but is not limited to, the solvent, the acrylate component, the reducing agent, and the light sensitive initiator.
  • the powder includes, but is not limited to, the basic component, a polyacrylate component, and the oxidizing agent, while the binder includes, but is not limited to, the solvent, the acidic component, the acrylate component, the reducing agent, and the light sensitive initiator.
  • the powder includes, but is not limited to, the basic component, an acidic component, a polyacrylate component, and the oxidizing agent, while the binder includes, but is not limited to, the solvent, another acidic component, the acrylate component, the reducing agent, and the light sensitive initiator.
  • FIG. 1 illustrates a block diagram of a representative SFF system 10 that includes, but is not limited to, a computer control system 12 , a dispensing system 14 , and a conventional curing system 16 .
  • the SFF system 10 can optionally include a positioning system, and a build platform temperature control system.
  • the computer control system 12 includes a process control system that is adapted to control the dispensing system 14 , the curing system 16 (e.g., a thermal, an ultraviolet, and/or a visible radiation curing system), the positioning system, and the build platform temperature control system.
  • the computer control system 12 includes, but is not limited to, a Computer Aided Design (CAD) system 16 or other SSF CAD-related systems.
  • CAD Computer Aided Design
  • the dispensing system 14 includes, but is not limited to, conventional powder spreading technologies, conventional inkjet technologies, conventional fluid coating technologies, and combinations thereof.
  • the components of the composition can be dispensed using one or more of these technologies in an iterative and/or simultaneous fashion.
  • the components of the composition can be dispensed independently of one another or in one or more combinations.
  • the powder is dispensed using conventional powder spreading techniques.
  • the powder spreading system includes a powder supply bin and a method for spreading the powder into a build bin where the object is being built. Examples of powder spreading systems are described in U.S. Pat. Nos. 5,340,656; 5,204,055 and 5,387,380, which are incorporated herein by reference.
  • the dispensing system 14 can include at least one conventional ink-jet printhead (e.g., thermal ink-jet printhead and/or a piezo ink-jet print head) adapted to dispense (e.g., jet) one or more components through one or more of a plurality of ink-jet printhead dispensers.
  • the ink-jet printhead can include a plurality of ink-jet compartments (e.g., tanks or wells for containing the components) that are capable of holding the components and are fluidically coupled to the ink-jet printhead dispensers.
  • the ink-jet printhead dispenser can be heated to assist in dispensing viscous components.
  • the in piezo-electric technologies the ink-jet printhead dispenser can be heated up to about 200° C., and preferably in the range of 70 to 120° C., while lower temperatures are used for thermal ink-jet technologies such as about 50-90° C.
  • the dispensing system 14 includes a separate ink-jet printhead for components (e.g., a binder, colorants, and solvents) of the composition.
  • components e.g., a binder, colorants, and solvents
  • one ink-jet printhead holds the binder and one ink-jet printhead holds the colorant.
  • the SFF system 10 can be incorporated into processes that are used to fabricate or construct three-dimensional objects in an iterative-layered process.
  • the computer control system 12 is capable of being selectively adjusted to control the output from the dispenser system 14 , which controls the thickness and pattern of each component in each layer of the iterative process.
  • the powder and the binder can be dispensed onto the build platform in a variety of patterns.
  • the patterns can take the form of, but not limited to, alternating layers of the powder and the binder.
  • the patterns of the powder and the binder can vary depending on the thickness of the powder, the particle size of the powder, and the volume (e.g., drops) of the binder.
  • multiple passes (e.g., scans) across the build platform 20 can be conducted to achieve the appropriate coverage of the powder and the binder.
  • the lower limit for the thickness of powder spread during each pass is limited by the size of the particles of the powder.
  • the powder particle size can be about 0.005 millimeters (mm) to 1 mm, about 10 to 100, and about 10 to 70.
  • the layer thickness can be from about 10 to 1000 microns and from about 25 to 100 microns.
  • the desirable amount of powder spread depends upon on a number of factors such as, but not limited to, the time required to build the object, the surface roughness, and the feature tolerance of the printed object.
  • the volume of the components dispensed using ink-jet technologies are from about 0.1 picoliters to 500 picoliters, about 0.1 picoliters to 100 picoliters, and about 0.1 picoliters to 35 picoliters.
  • the desirable ejected volume of these components depends on a number of factors such as, but not limited to, the concentration and the chemical characteristics of the components; the temperature of the components, the desired resolution (e.g., 600 drops per inch), and the design of the print-head firing chamber.
  • FIG. 2 is a flow diagram describing a representative method 30 for forming an object using the SFF system 10 .
  • the powder and the binder are provided, as shown in block 22 .
  • the powder and the binder are dispensed onto the build platform in a layer-by-layer fashion, as shown in block 24 .
  • the powder is first spread onto the build platform using a roller.
  • the binder is dispensed onto portions of the powder as controlled by the computer system 12 .
  • the powder and the binder are commingled and form a layer of the composition.
  • the three-dimensional object is formed, as shown in block 26 .
  • the powder and the binder should be able to react to form a “tack free” layer within about 5 seconds to 10 minutes at a temperature below about 100° C.
  • the powder and the binder should be able to react to form a “tack free” layer within about 5 seconds to 1 minute at a temperature below about 60° C.
  • tack free is defined as the point where the crosslinking/chain growth reaction has progressed such that the resulting material is no longer tacky to the touch. It does not imply that chain growth is complete.
  • one or more chemical interactions can be used to describe the chemistry of the composition.
  • the chemical interactions include, but are not limited to, a acid/base hardening mechanism, a chemically activated polymerization mechanism, a light activated polymerization mechanism, and combinations thereof, each of which are briefly described below.
  • the acid component is soluble in the binder (e.g., a polar binder, where the acid compound is acidic relative to water).
  • the binder e.g., a polar binder, where the acid compound is acidic relative to water.
  • the released cations from the basic component mediate the crosslinking of the compounds that make up the acid component.
  • Ionic crosslinking of the acidic compounds reduces the mobility of the acid component.
  • the crosslinking process results in solidification of the acid component in the solution, followed by setting and further hardening of the material.
  • the acid/base hardening mechanism facilitates curing by ionic reactions like neutralization, salt formation, chelation, and/or crystallization
  • the chemically activated polymerization mechanism includes the redox reaction between the reducing agent with the oxidizing agent. Interaction of the reducing agent with the oxidizing agent causes the oxidizing agent to form a radical oxidizing agent.
  • the radical oxidizing agent initiates the polymerization of the one or more acrylates to produce polymeric forms of the given monomers.
  • redox reaction systems of this type can be found in U.S. Pat. Nos. 5,154,762 and 6,136,885, which are included herein by reference.
  • the light activated polymerization mechanism includes the interaction of the light sensitive initiator with light (e.g., ultraviolet and/or visible light) from a light source (e.g., the curing system 16 ). Interaction of the light with the light sensitive initiator causes the light sensitive initiator to form a radical initiator.
  • the radical initiator initiates the polymerization of the one or more acrylates to produce polymeric forms of the given monomers.
  • any combination of the acid/base hardening mechanism, the chemically activated polymerization mechanism, and the light activated polymerization mechanism can be used to form each layer of the three-dimensional object.
  • the polymerization of the acrylate components can be activated by one or both of the chemically activated polymerization and the light activated polymerization mechanisms.
  • the acid/base hardening mechanism, the chemically activated polymerization mechanism, and/or the light activated polymerization mechanism provides a non-porous three-dimensional object having superior compressive strength and significantly better mechanical properties relative to common systems typically used in SFF systems.
  • the need for post-processing the three-dimensional object is decreased and eliminated in some instances.
  • the acid/base hardening mechanism and polymerizations mechanisms are fast, which minimizes diffusion of the binder into the surrounding powder and thus providing a continuous texture and finish.
  • the light activated polymerization mechanism is controllable by exposure time and applied energy.
  • the acid component can include compounds having molecular weights from about 20,000-1,000,000 g/mol.
  • the acid component can include, but is not limited to, alginic acid, gum arabic, nucleic acids, pectins, proteins (biopolymers), carboxymethylcellulose, ligninsulphonic acids, acid-modified starch (chemically modified biopolymers), polymethacrylic acid, polymethacrylic acid copolymer with methyl methacrylate, polyvinyl sulphonic acid, polystyrene sulphonic acid, polysulphuric acid, polyvinyl phosphonic acid, polyvinyl phosphoric acid, the homo- and copolymers of unsaturated aliphatic carbonic acids such as acrylic acid, itaconic acid, mesaconic acid, citraconic acid, aconitic acid, maleic acid, fumaric acid, glutaconic acid, tiglic acid and methacrylic acid and the anhydrides of these carbonic acids (e
  • polycarbonic acid anhydrides form precursors of the polycarbonic acids, which are transferred by water contact into polycarbonic acid.
  • suitable polyacid components include, but are not limited to, the copolymers of the polyacids with acrylic amide, acrylic nitrile, acrylic acid esters, vinyl chloride, allyl chloride, vinyl acetate and 2-hydroxyethyl methacrylate (synthetic polyelectrolytes).
  • the acid component could be partially or fully substituted with unsaturated polymerizable acidic moieties of a monomeric or oligomeric nature, as well as their salts or other acid derivative groups.
  • Polymerizable unsaturated monomers, oligomers or prepolymers with acid groups or reactive acid-derivative groups include, but is not limited to:
  • the reactive acid derivatives can be substituted with acid halides, with acid anhydrides, and with acid amides, nitrites, and esters, that readily hydrolyze into acid, as such can enter into ion-exchange, neutralization, salt formation, or chelation reactions with the base component (e.g., metal oxides, ceramics, zeolites or leachable reactive glasses).
  • the base component e.g., metal oxides, ceramics, zeolites or leachable reactive glasses.
  • acid groups or reactive acid derivatives include carboxylate, phosphate, phosphonate, sulfonate, or borate acid radicals or of their reactive derivatives.
  • the polymerizable unsaturated monomers, oligomers, or prepolymers of the acid component can include, but is not limited to, one or more of the following groups: alkenyl groups, alkenoxy groups, cycloalkenyl groups, aralkenyl groups, or alkenaryl radicals groups, with acryl, methacryl, vinyl, or styryl radicals being preferable.
  • Preferred compounds are those that contain at least two polymerizable groups or at least two acid groups or acid-derivative groups. Examples are phosphoric-acid esters of glycerine dimethacrylate or 1-methacryloxyethane-1,1-diphosphonic acid.
  • the composition can include the acid component from 1% to about 40% and from about 5% to about 30% by weight of the composition.
  • the basic component can include, but is not limited to, a metal oxide (e.g., Ca, Al, Fe, and Ba) and salts thereof and reactive glasses (e.g., silanized reactive aluminosilicate, calcium aluminosilicate and calcium aluminum glass).
  • the composition can include the basic component from 20% to about 80% and from about 30% to about 70% by weight of the composition.
  • acid-base combinations include, but are not limited to, the following.
  • Zinc oxide polycarboxylic acid cements.
  • Metal oxide e.g., Be, Zn, Cu, Mg, Ca, Sr, and Ba
  • metal cations crosslink phosphate anions resulting in the formation of a hydrogel matrix.
  • setting of the cement involves the formation of a hydrogel matrix of silica gel and ionically crosslinked phosphate ions.
  • the average particle size for the glass is preferably approximately 30 ⁇ m or less, as glass particles with a smaller diameter can be difficult to spread.
  • Oxysalt-bonded cements These are formed by acid-base reactions of metal oxide powder such as ZnO or MgO, and a concentrated solution of metal chloride or sulfate where the metal is, for example, Zn or Mg.
  • the basic component of the system is reactive aluminosilicate glass and the acidic component of the system is organic polyacid containing functional groups such as —COOH, —SO 3 H, and —PO 3 H 2 .
  • the glass ionomer mixture may also contain small amounts of low molecular weight complexing agent such as L- or D-tartaric acid for adjusting the kinetics of the cement setting process.
  • the glass-ionomer cements should be pretreated to make the surface of the polyacid powder less hydrophilic and therefore less susceptible to clumping due to moisture absorption.
  • a preferable pretreatment includes the addition of some anti-caking hydrophobic agent to the dry cement mix.
  • the agent could include some stearate salts (e.g., Mg, Ca, and Zn) or lecithin.
  • the acrylate component can include, but is not limited to, mono-functional acrylates, di-functional acrylates, tri-functional acrylates, tetra-functional acrylates, and combinations thereof.
  • the acrylate can include, but is not limited to, water-soluble mono-, di-, and polymethacrylates with a low viscosity.
  • the acrylate component can include, but is not limited to, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol monomethacrylates (e.g.
  • the acrylate component can also include, but is not limited to, metal salts of methacrylate and acrylate.
  • the acrylate component can include, but is not limited to, sodium methacrylate, potassium methacrylate, ammonium methacrylate, magnesium methacrylate, calcium methacrylate, aluminum methacrylate, zinc methacrylate, zirconium methacrylate, zirconium trihydroxymonomethacrylate, zirconium dihydroxydimethacrylate, sodium acrylate, potassium acrylate, ammonium acrylate, magnesium acrylate, calcium acrylate, aluminum acrylate, zinc acrylate, zirconium acrylate, zirconium trihydroxymonoacrylate, and zirconium dihydroxyacrylate.
  • the acrylate component can also include, but is not limited to, acrylates having ethylenically unsaturated groups and acid groups (e.g., —COOH) or ethylenically unsaturated groups, acid groups (e.g., —COOH) and base groups (e.g., —NH 2 ) in one component.
  • the acrylates having ethylenically unsaturated groups also include the acid esters that can be formed from the above-stated mono- and dimethacrylates.
  • the composition can include the acrylate component from 5% to about 50% and from about 20% to about 50% by weight of the composition.
  • the reducing agent can include chemicals such as, but not limited to, a water-soluble amine, metal salts, hydrazines, and combinations thereof.
  • the reducing agent-can include chemicals such as, but not limited to, dimethyl-p-toluidine, dihydroxyethyl-p-toluidine and N,N-dimethylaminobenzoate, and combinations thereof.
  • the composition can include the reducing agent from 0.1% to about 10% and from about 1% to about 5% by weight of the composition.
  • the oxidizing agent can include chemicals such as, but not limited to, persulphates, benzoyl peroxides, hydroperoxides, cobalt (III) and iron (III) salts, and hydrogen peroxides, and combinations thereof.
  • the oxidizing agent can include chemicals such as, but not limited to, benzoyl peroxides.
  • the composition can include the oxidizing agent from 0.1% to about 10% and from about 1% to about 5% by weight of the composition.
  • the light sensitive initiator can include, but is not limited to, UV initiators and/or visible initiators.
  • the UV initiator can include chemicals such as, but not limited to, a free radical initiator, a cationic initiator, or combinations thereof.
  • the free-radical initiator includes compounds that produce a free radical on exposure to UV radiation. The free-radical is capable of initiating a polymerization reaction.
  • Exemplar free-radical initiators include, but are not limited to, benzophenones (e.g., benzophenone, methyl benzophenone, Michler's ketone, and xanthones), acylphosphine oxide type free radical initiators (e.g., 2,4,6-trimethylbenzoyldiphenyl phosphine oxide (TMPO), 2,4,6-trimethylbenzoylethoxyphenyl phosphine oxide (TEPO), and bisacylphosphine oxides (BAPO's)), azo compounds (e.g., AlBN), benzoins, and bezoin alkyl ethers (e.g., benzoin, benzoin methyl ether and benzoin isopropyl ether).
  • benzophenones e.g., benzophenone, methyl benzophenone, Michler's ketone, and xanthones
  • acylphosphine oxide type free radical initiators e.
  • the free-radical initiator can be used alone or in combination with a co-initiator.
  • Co-initiators are used with initiators that need a second molecule to produce a radical that is active in UV-systems.
  • benzophenone uses a second molecule, such as an amine, to produce a reactive radical.
  • a preferred class of co-initiators are alkanolamines such as, but not limited to, triethylamine, methyldiethanolamine and triethanolamine
  • Suitable cationic initiators include, but are not limited to, compounds that form aprotic acids or Bronsted acids upon exposure to UV light sufficient to initiate polymerization.
  • the cationic initiator used may be a single compound, a mixture of two or more active compounds, or a combination of two or more different compounds (e.g., co-initiators).
  • Exemplary cationic initiators include, but are not limited to, aryldiazonium salts, diaryliodonium salts, triarylsulphonium salts, and triarylselenium salts.
  • the visible radiation initiator can include, but is not limited to, diketones (e.g., camphorquinone, 1,2-acenaphthylenedione, 1H-indole-2,3-dione, 5H-dibenzo[a,d]cycloheptene-10, and 11-dione), phenoxazine dyes (e.g., Resazurin, Resorufin), acylphosphine oxides, (e.g., diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide), and the like.
  • diketones e.g., camphorquinone, 1,2-acenaphthylenedione, 1H-indole-2,3-dione, 5H-dibenzo[a,d]cycloheptene-10, and 11-dione
  • phenoxazine dyes e.g., Resazurin, Res
  • the composition can include the light sensitive initiator from 0.01% to about 5% and from about 0.01% to about 3% by weight of the composition.
  • the binder functions to, at least, as a solvent.
  • the binder functions to stimulate a crosslinking reaction between the basic component and the acidic component.
  • binder is capable of stimulating polymerization reaction between the acrylate component, the radical initiator, and the oxidizing agent.
  • the binder can be a polar binder or a non-polar binder.
  • the polar binder can include, but is not limited to, water, ethanol, hexanediol, pentanediol, water-soluble acryates and combinations thereof.
  • the non-polar binder can include, but is not limited to, silanes, dimethylsilicone, chlorinated organic solvents (such as chloroform, carbon tetrachloride, o-dichlorobenzene), aliphatic alcohols, cyclohexane, dimethylaniline, triethylamine, 1,4-cyclohexadiene, and combinations thereof.
  • chlorinated organic solvents such as chloroform, carbon tetrachloride, o-dichlorobenzene
  • aliphatic alcohols such as chloroform, carbon tetrachloride, o-dichlorobenzene
  • aliphatic alcohols such as cyclohexane, dimethylaniline, triethylamine, 1,4-cyclohexadiene, and combinations thereof.
  • the powder and/or the binder can include additional components such as, but not limited to, retardants, inhibitors, wetting agents, viscosity modifiers, surface tension modifiers, colorants (e.g., dyes, pigments, inks), dispersants, antioxidants, water retaining additives, accelerators, humectants, solvents, and combinations thereof.
  • additional components such as, but not limited to, retardants, inhibitors, wetting agents, viscosity modifiers, surface tension modifiers, colorants (e.g., dyes, pigments, inks), dispersants, antioxidants, water retaining additives, accelerators, humectants, solvents, and combinations thereof.
  • Additional components can be used in the powder and/or the binder to obtain the proper balance of cure rate, layer-to-layer adhesion, toughness, and glass transition temperature, of the three-dimensional object. Furthermore, the components can be used to alter the physical and/or chemical properties (e.g., viscosity, reactivity, surface tension, bubble formation, and wetting of the ejection chamber) of the powder and/or the binder prior to and/or after being dispensed.
  • physical and/or chemical properties e.g., viscosity, reactivity, surface tension, bubble formation, and wetting of the ejection chamber
  • the retardant functions to, at least, slow down the setting reaction of the polyacid and the crosslinking multivalent cations.
  • the retardant can include, but is not limited to, sodium phosphate, potassium phosphate, potassium oxalate, sodium oxalate, sodium carbonate, potassium carbonate, salicylic acid, tartaric acid, dihydroxytartaric acid, oxalic acid, citric acid, ethylenediamine tetraacetic acid (EDTA) and their sodium and potassium salts, sodium phosphate, sodium dihydrogen phosphate as well as sodium hydrogen phosphate, magnesium oxide and tin fluoride and combinations thereof.
  • the composition can include the retardant from 1% to about 10% and from about 2% to about 8% by weight of the composition.
  • the inhibitor functions to, at least, quench premature curing reactions.
  • the inhibitor can include, but is not limited to, t-butylhydroxy toluene, methyl ethyl ketone, and combinations thereof.
  • the composition can include the inhibitor from 0.01% to about 1% and from about 0.01% to about 0.1% by weight of the composition.
  • the accelerator functions to, at least, crosslink with the acid component and/or the acrylate component and enhances the physical property of the three-dimensional object.
  • the accelerator can form compounds such as, but not limited to, Al 3+ compounds (e.g., Al(NO 3 ) 3 , Al 2 (PO 4 ) 3 , and Al 2 (SO 4 ) 3 ) and Zn 2+ compounds (e.g., ZnO, Zn(NO 3 ) 2 , and Zn(SO 4 )).
  • the composition can include the accelerator from 0.1% to about 10% and from about 1% to about 5% by weight of the composition.
  • the wetting agent functions to, at least, wet the resistor.
  • the wetting agent can include, but is not limited to, tergitols, ethylene glycols, and fluorosurfactants, and combinations thereof.
  • the composition can include the wetting agent from 0 . 0 1% to about 3% and from about 0.1% to about 1% by weight of the composition.
  • the viscosity modifier functions to, at least, increase or decrease the viscosity of the binder composition.
  • the viscosity modifier can include, but is not limited to, ethanol, hexanediol, pentanediol, ethylene glycol diacetate, potassium aluminum sulphate, isopropanol, ethylene glycol monobutyl ether, diethylene monobutyl ether, dodecyldimethylammonium proposane sulphonate, glycerine triacetate, ethyl acetoacetate, polyvinyl pyrrolidone, polyethylene glycol, polyacrylic acid, sodium polyacrylate, and combinations thereof.
  • the composition can include the viscosity modifier from 1% to about 30% and from about 5% to about 20% by weight of the composition.
  • the surface tension modifier functions to, at least, increase or decrease the surface tension of the binder composition.
  • the surface tension modifier functions to clear the inkjet orifice plate of extraneous liquid that might interfere with drop ejection.
  • the surface tension modifier can include, but is not limited to, ethanol, hexanediol, pentanediol, tergitols, ethylene glycols, fluorosurfactants, and combinations thereof.
  • the composition can include the surface tension modifier from 0.01% to about 30% and from about 0.1% to about 20% by weight of the composition.
  • the addition of fibers to the powder may be performed to vary and/or improve the mechanical properties (e.g., bending strength and fracture toughness) of the three-dimensional object.
  • the fibers can include, but are not limited to, polymer fibers, ceramic fibers, natural fibers, carbon fibers, glass fibers, and combinations thereof. More specifically, the fibers can include, but are not limited to, cellulose fibers, wood fibers, polypropylene fibers, aramide fibers, silicon carbide fibers, aluminum silicate fibers, and derivative of each of these exemplary fibers.
  • the powder can include fibers from 1% to about 30% and from about 3% to about 20% by weight of the composition.
  • the addition of filler functions to, at least, stiffen and smooth the surface of-the three-dimensional object.
  • the fillers can include organic fillers and inorganic fillers.
  • the organic fillers can include, but are not limited to, methacrylates (e.g., polymethylmethacrylate and polyhydroxyethylmethacrylate), polybutadiene styrene copolymers, maleic anhydride co-polymers, starch, starch derivatives, cellulose, cellulose derivatives, polycarbonates, polyepoxides, polyacrylates, polymethacryaltes, polyethylene and combinations thereof.
  • the inorganic fillers can include, but are not limited to, fumed silica, hydroxyapatite, layered double hydroxides, organic-inorganic clays ceramics, glasses, naturally occurring materials and their synthetic derivatives, polymer fillers, sand, quartz, silicon dioxide, aluminum oxide, titanium dioxide, aluminum hydroxide, nitrides (e.g. silicon nitride), kaolin, talc, wollstonite, feldspar, mica, zinc glass, boron silicate glass, and combinations thereof.
  • the composition can include the filler from 1% to about 60% and from about 10% to about 50% by weight of the composition.
  • ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
  • concentration range of “about 0.1% to about 5%” should be interpreted to include not only the explicitly recited concentration of about 0.1 wt % to about 5 wt %, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%) within the indicated range.

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Abstract

Chemical compositions are disclosed. One exemplary composition, among others, includes: a basic component, an acidic component, at least one acrylate component, oxidizing agent, reducing agent, and a binder. The binder includes a viscosity modifier and a surface tension modifier. The binder is capable of stimulating a reaction between the basic component and the acidic component. A portion of the binder is capable of undergoing a polymerization reaction between at least one acrylate component, the oxidizing agent, and the reducing agent. The polymerization reaction being initiated by the redox reaction between the oxidizing agent and the reducing agent.

Description

BACKGROUND
Solid freeform fabrication (SFF) or layer manufacturing (LM) is a fabrication technology that builds an object of any complex shape layer by layer or point by point without using a pre-shaped tool (die or mold). This process begins with creating a Computer Aided Design (CAD) file to represent the geometry of a desired object. SFF technology enables direct translation of the CAD image data into a three-dimensional object. SFF technology can be used in applications such as verifying CAD database, evaluating design feasibility, testing part functionality, assessing aesthetics, checking ergonomics of design, aiding in tool and fixture design, creating conceptual models and sales/marketing tools, generating patterns for investment casting, reducing or eliminating engineering changes in production, and providing small production runs.
One SFF technique involves adding or depositing a build composition to form predetermined areas of a layer essentially point-by-point. These predetermined areas together constitute a thin section of a three-dimensional object as defined by a CAD geometry. Successive layers are then deposited in a predetermined sequence with a layer being affixed to its adjacent layers forming an integral three dimensional, multi-layer object.
In a powder/binder SFF system an individual layer is printed by first spreading a thin layer of the powder and then dispensing the binder to adhere the powder together in selected regions to create the desired layer pattern. This process is repeated until all the layers have been printed. The binder joins powder together within a layer and between layers. After printing is complete, the unbound powder is removed, leaving a three-dimensional object with the desired geometry.
SUMMARY
Briefly described, embodiments of this disclosure include compositions. One exemplary composition of this disclosure includes a basic component, an acidic component, at least one acrylate component, oxidizing agent, reducing agent, and a binder. The binder includes a viscosity modifier and a surface tension modifier. The binder is capable of stimulating a reaction between the basic component and the acidic component. A portion of the binder is capable of undergoing a polymerization reaction between at least one acrylate component, the oxidizing agent, and the reducing agent. The polymerization reaction being initiated by the redox reaction between the oxidizing agent and the reducing agent.
BRIEF DESCRIPTION OF THE DRAWINGS
Many aspects of this disclosure can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.
FIG. 1 illustrates an embodiment of a solid freeform fabrication (SFF) system.
FIG. 2 illustrates a flow diagram of a representative embodiment for forming a three-dimensional object using the SFF system described in FIG. 1
DETAILED DESCRIPTION
Compositions that can be used in solid freeform fabrication (SFF) systems are provided. In general, the embodiments relate to the use of the compositions in the manufacture of three-dimensional objects. The term three-dimensional object refers to objects that are sufficiently rigid to maintain a fixed volume and shape to an extent, which is appropriate for the specific use.
Embodiments of the composition can include components such as, but not limited to, a basic component, an acidic component, at least one acrylate component (e.g., mono-, di-, tri-, tetra-acrylate compounds), an oxidizing agent, a reducing agent, a light sensitive initiator, and combinations thereof. Embodiments disclosed herein include a plurality of combinations of components and exemplar combinations are described below.
For example, one embodiment of the composition includes, but is not limited to, the basic component, the acidic component, one or more acrylate components, the oxidizing agent, and the reducing agent. Another embodiment of the composition includes, but is not limited to, the basic component, the acidic component, one or more acrylate components, and the light sensitive initiator. Still another embodiment of the composition includes, but is not limited to, the basic component, the acidic component, one or more acrylate components, the oxidizing agent, the reducing agent, and the light sensitive initiator. In addition, the composition can include additional components such as, but not limited to, retardants, wetting agents, viscosity modifiers, surface tension modifiers, fibers, colorants, dispersants, antioxidants, organic and inorganic fillers, solvents, and combinations thereof.
The components of the composition can be included in a powder and/or a binder. The ratio of binder to powder can be from about 0.05:1 to 0.6:1, and from about 0.1:1 to 0.4:1. The ratio of binder to powder depends upon many variables such as, but not limited to, the components, the concentration of each component, and the percentage of each component in the powder; the components, the concentration of each component, and the percentage of each component in the binder; and combinations thereof.
Various combinations of components in the powder and/or the binder are feasible and the following illustrate exemplar embodiments. For example, in one embodiment the powder includes, but is not limited to, the basic component, the acidic component, a polyacrylate component, and the oxidizing agent, while the binder includes, but is not limited to, a solvent (e.g., a polar solvent such as water), an acrylate component (e.g., monomeric acrylate), and the reducing agent.
Another embodiment of the powder includes, but is not limited to, the basic component, a polyacrylate component, and the oxidizing agent while the binder includes, but is not limited to, the solvent, the acidic component, the acrylate component, and the reducing agent.
In still another embodiment, the powder includes, but is not limited to, the basic component, an acidic component, a polyacrylate component, and the oxidizing agent, while the binder includes, but is not limited to, the solvent, another acidic component, the acrylate component, and the reducing agent.
In still another embodiment, the powder includes, but is not limited to, the basic component, the acidic component and a polyacrylate component, while the binder includes, but is not limited to, the solvent, the acrylate component, and the light sensitive initiator.
In still another embodiment, the powder includes, but is not limited to, the basic component and a polyacrylate component, while the binder includes, but is not limited to, the solvent, the acidic component, the acrylate component, and the light sensitive initiator.
In still another embodiment, the powder includes, but is not limited to, the basic component, an acidic component, and a polyacrylate component, while the binder includes, but is not limited to, the solvent, another acidic component, the acrylate component, and the light sensitive initiator.
In still another embodiment, the powder includes, but is not limited to, the basic component, the acidic component, a polyacrylate component, and the oxidizing agent, while the binder includes, but is not limited to, the solvent, the acrylate component, the reducing agent, and the light sensitive initiator.
In still another embodiment, the powder includes, but is not limited to, the basic component, a polyacrylate component, and the oxidizing agent, while the binder includes, but is not limited to, the solvent, the acidic component, the acrylate component, the reducing agent, and the light sensitive initiator.
In still another embodiment, the powder includes, but is not limited to, the basic component, an acidic component, a polyacrylate component, and the oxidizing agent, while the binder includes, but is not limited to, the solvent, another acidic component, the acrylate component, the reducing agent, and the light sensitive initiator.
FIG. 1 illustrates a block diagram of a representative SFF system 10 that includes, but is not limited to, a computer control system 12, a dispensing system 14, and a conventional curing system 16. In addition, the SFF system 10 can optionally include a positioning system, and a build platform temperature control system. The computer control system 12 includes a process control system that is adapted to control the dispensing system 14, the curing system 16 (e.g., a thermal, an ultraviolet, and/or a visible radiation curing system), the positioning system, and the build platform temperature control system. Furthermore, the computer control system 12 includes, but is not limited to, a Computer Aided Design (CAD) system 16 or other SSF CAD-related systems.
The dispensing system 14 includes, but is not limited to, conventional powder spreading technologies, conventional inkjet technologies, conventional fluid coating technologies, and combinations thereof. The components of the composition can be dispensed using one or more of these technologies in an iterative and/or simultaneous fashion. In addition, the components of the composition can be dispensed independently of one another or in one or more combinations.
In one embodiment, the powder is dispensed using conventional powder spreading techniques. The powder spreading system includes a powder supply bin and a method for spreading the powder into a build bin where the object is being built. Examples of powder spreading systems are described in U.S. Pat. Nos. 5,340,656; 5,204,055 and 5,387,380, which are incorporated herein by reference.
Ink-jet technology, such as drop-on-demand and continuous flow ink-jet technologies, can be used to dispense components of the composition onto a build platform. The dispensing system 14 can include at least one conventional ink-jet printhead (e.g., thermal ink-jet printhead and/or a piezo ink-jet print head) adapted to dispense (e.g., jet) one or more components through one or more of a plurality of ink-jet printhead dispensers. In addition, the ink-jet printhead can include a plurality of ink-jet compartments (e.g., tanks or wells for containing the components) that are capable of holding the components and are fluidically coupled to the ink-jet printhead dispensers. The ink-jet printhead dispenser can be heated to assist in dispensing viscous components. For example, the in piezo-electric technologies the ink-jet printhead dispenser can be heated up to about 200° C., and preferably in the range of 70 to 120° C., while lower temperatures are used for thermal ink-jet technologies such as about 50-90° C.
In one embodiment, the dispensing system 14 includes a separate ink-jet printhead for components (e.g., a binder, colorants, and solvents) of the composition. For example, in a SFF system 10 having two ink-jet printheads, one ink-jet printhead holds the binder and one ink-jet printhead holds the colorant.
The SFF system 10 can be incorporated into processes that are used to fabricate or construct three-dimensional objects in an iterative-layered process. The computer control system 12 is capable of being selectively adjusted to control the output from the dispenser system 14, which controls the thickness and pattern of each component in each layer of the iterative process.
For example, the powder and the binder can be dispensed onto the build platform in a variety of patterns. The patterns can take the form of, but not limited to, alternating layers of the powder and the binder. In addition, the patterns of the powder and the binder can vary depending on the thickness of the powder, the particle size of the powder, and the volume (e.g., drops) of the binder. In this regard, multiple passes (e.g., scans) across the build platform 20 can be conducted to achieve the appropriate coverage of the powder and the binder.
In general, the lower limit for the thickness of powder spread during each pass is limited by the size of the particles of the powder. The powder particle size can be about 0.005 millimeters (mm) to 1 mm, about 10 to 100, and about 10 to 70. The layer thickness can be from about 10 to 1000 microns and from about 25 to 100 microns. However, the desirable amount of powder spread depends upon on a number of factors such as, but not limited to, the time required to build the object, the surface roughness, and the feature tolerance of the printed object. In general, the volume of the components dispensed using ink-jet technologies are from about 0.1 picoliters to 500 picoliters, about 0.1 picoliters to 100 picoliters, and about 0.1 picoliters to 35 picoliters. However, the desirable ejected volume of these components depends on a number of factors such as, but not limited to, the concentration and the chemical characteristics of the components; the temperature of the components, the desired resolution (e.g., 600 drops per inch), and the design of the print-head firing chamber.
FIG. 2 is a flow diagram describing a representative method 30 for forming an object using the SFF system 10. The powder and the binder are provided, as shown in block 22. The powder and the binder are dispensed onto the build platform in a layer-by-layer fashion, as shown in block 24. For example, the powder is first spread onto the build platform using a roller. Then the binder is dispensed onto portions of the powder as controlled by the computer system 12. The powder and the binder are commingled and form a layer of the composition. After a plurality of layers of the powder and the binder are dispensed onto the build platform, the three-dimensional object is formed, as shown in block 26.
The powder and the binder should be able to react to form a “tack free” layer within about 5 seconds to 10 minutes at a temperature below about 100° C. Preferably, the powder and the binder should be able to react to form a “tack free” layer within about 5 seconds to 1 minute at a temperature below about 60° C. The term “tack free” is defined as the point where the crosslinking/chain growth reaction has progressed such that the resulting material is no longer tacky to the touch. It does not imply that chain growth is complete.
Although not intending to be bound by theory, one or more chemical interactions can be used to describe the chemistry of the composition. The chemical interactions include, but are not limited to, a acid/base hardening mechanism, a chemically activated polymerization mechanism, a light activated polymerization mechanism, and combinations thereof, each of which are briefly described below.
In the acid/base hardening mechanism, the acid component is soluble in the binder (e.g., a polar binder, where the acid compound is acidic relative to water). Thus, contact of the acidic component with the binder causes protons to dissociate from the acidic component. The free protons are attracted to the basic component and the basic component releases multivalent cations as the protons replace the cations.
The released cations from the basic component mediate the crosslinking of the compounds that make up the acid component. Ionic crosslinking of the acidic compounds reduces the mobility of the acid component. Eventually the crosslinking process results in solidification of the acid component in the solution, followed by setting and further hardening of the material. The acid/base hardening mechanism facilitates curing by ionic reactions like neutralization, salt formation, chelation, and/or crystallization
The chemically activated polymerization mechanism includes the redox reaction between the reducing agent with the oxidizing agent. Interaction of the reducing agent with the oxidizing agent causes the oxidizing agent to form a radical oxidizing agent. The radical oxidizing agent initiates the polymerization of the one or more acrylates to produce polymeric forms of the given monomers. For example, redox reaction systems of this type can be found in U.S. Pat. Nos. 5,154,762 and 6,136,885, which are included herein by reference.
The light activated polymerization mechanism includes the interaction of the light sensitive initiator with light (e.g., ultraviolet and/or visible light) from a light source (e.g., the curing system 16). Interaction of the light with the light sensitive initiator causes the light sensitive initiator to form a radical initiator. The radical initiator initiates the polymerization of the one or more acrylates to produce polymeric forms of the given monomers.
It should be noted that any combination of the acid/base hardening mechanism, the chemically activated polymerization mechanism, and the light activated polymerization mechanism can be used to form each layer of the three-dimensional object. In particular, the polymerization of the acrylate components can be activated by one or both of the chemically activated polymerization and the light activated polymerization mechanisms.
The acid/base hardening mechanism, the chemically activated polymerization mechanism, and/or the light activated polymerization mechanism provides a non-porous three-dimensional object having superior compressive strength and significantly better mechanical properties relative to common systems typically used in SFF systems. In addition, the need for post-processing the three-dimensional object is decreased and eliminated in some instances. Further, the acid/base hardening mechanism and polymerizations mechanisms are fast, which minimizes diffusion of the binder into the surrounding powder and thus providing a continuous texture and finish. Furthermore, the light activated polymerization mechanism is controllable by exposure time and applied energy.
Now having described embodiments of this disclosure, exemplary chemicals for the acid component, the basic component, the acrylate component, the binder, the oxidizing agent, the reducing agent, and the light sensitive initiator, are described below.
In general, the acid component can include compounds having molecular weights from about 20,000-1,000,000 g/mol. In particular, the acid component can include, but is not limited to, alginic acid, gum arabic, nucleic acids, pectins, proteins (biopolymers), carboxymethylcellulose, ligninsulphonic acids, acid-modified starch (chemically modified biopolymers), polymethacrylic acid, polymethacrylic acid copolymer with methyl methacrylate, polyvinyl sulphonic acid, polystyrene sulphonic acid, polysulphuric acid, polyvinyl phosphonic acid, polyvinyl phosphoric acid, the homo- and copolymers of unsaturated aliphatic carbonic acids such as acrylic acid, itaconic acid, mesaconic acid, citraconic acid, aconitic acid, maleic acid, fumaric acid, glutaconic acid, tiglic acid and methacrylic acid and the anhydrides of these carbonic acids (e.g. itaconic acid anhydride). These polycarbonic acid anhydrides form precursors of the polycarbonic acids, which are transferred by water contact into polycarbonic acid. Further suitable polyacid components include, but are not limited to, the copolymers of the polyacids with acrylic amide, acrylic nitrile, acrylic acid esters, vinyl chloride, allyl chloride, vinyl acetate and 2-hydroxyethyl methacrylate (synthetic polyelectrolytes).
In one embodiment, the acid component could be partially or fully substituted with unsaturated polymerizable acidic moieties of a monomeric or oligomeric nature, as well as their salts or other acid derivative groups. Polymerizable unsaturated monomers, oligomers or prepolymers with acid groups or reactive acid-derivative groups include, but is not limited to:
a. unsaturated organic esters of phosphoric and phosphonic acids (German AS No. 2 711 234 & German OS No. 3 150 285, both are incorporated herein by reference),
b. unsaturated organic esters of monofluorophosphoric acid (U.S. Pat. No. 3,997,504, incorporated herein by reference),
c. unsaturated organic esters of phosphoric acids that contain either chlorine or bromine bonded directly to the phosphorus (Eur. Pat. No. 0 058 483, incorporated herein by reference),
d. unsaturated organic esters of phosphoric acid in the form of pyrophosphates (anhydrides) (German OS No. 3 048 410, incorporated herein by reference),
e. unsaturated carboxylic acids,
f. unsaturated sulfur-containing organic acid moieties with groups of —SO2H, —SO3H, —O—SO3H type,
g. unsaturated organic derivatives of boric acid i.e. the ones containing groups: —B(OH)2, B(OH)(OR), —O—B(OH)2, —O—B(OH)(OR) wherein R is H or alkyl,
h. unsaturated organic moieties containing cationic acid radicals like NR2H+, —RR2H+ (wherein R is H or alkyl), and/or
i. unsaturated organic moieties containing different combinations of the acidic species listed in the a)-h).
The reactive acid derivatives can be substituted with acid halides, with acid anhydrides, and with acid amides, nitrites, and esters, that readily hydrolyze into acid, as such can enter into ion-exchange, neutralization, salt formation, or chelation reactions with the base component (e.g., metal oxides, ceramics, zeolites or leachable reactive glasses). Preferred are acid groups or reactive acid derivatives include carboxylate, phosphate, phosphonate, sulfonate, or borate acid radicals or of their reactive derivatives.
The polymerizable unsaturated monomers, oligomers, or prepolymers of the acid component can include, but is not limited to, one or more of the following groups: alkenyl groups, alkenoxy groups, cycloalkenyl groups, aralkenyl groups, or alkenaryl radicals groups, with acryl, methacryl, vinyl, or styryl radicals being preferable. Preferred compounds are those that contain at least two polymerizable groups or at least two acid groups or acid-derivative groups. Examples are phosphoric-acid esters of glycerine dimethacrylate or 1-methacryloxyethane-1,1-diphosphonic acid. The composition can include the acid component from 1% to about 40% and from about 5% to about 30% by weight of the composition.
The basic component can include, but is not limited to, a metal oxide (e.g., Ca, Al, Fe, and Ba) and salts thereof and reactive glasses (e.g., silanized reactive aluminosilicate, calcium aluminosilicate and calcium aluminum glass). The composition can include the basic component from 20% to about 80% and from about 30% to about 70% by weight of the composition.
Examples of acid-base combinations include, but are not limited to, the following.
a. Zinc oxide—polycarboxylic acid cements.
b. Metal oxide (e.g., Be, Zn, Cu, Mg, Ca, Sr, and Ba)—orthophosphoric or poly(phosphoric acid) cements. In this embodiment, metal cations crosslink phosphate anions resulting in the formation of a hydrogel matrix.
c. A mixture of reactive aluminosilicate glasses with orthophosphoric or poly(phosphoric acid). In this embodiment, setting of the cement involves the formation of a hydrogel matrix of silica gel and ionically crosslinked phosphate ions. The average particle size for the glass is preferably approximately 30 μm or less, as glass particles with a smaller diameter can be difficult to spread.
d. Oxysalt-bonded cements. These are formed by acid-base reactions of metal oxide powder such as ZnO or MgO, and a concentrated solution of metal chloride or sulfate where the metal is, for example, Zn or Mg.
e. Glass-ionomer cements. In this embodiment, the basic component of the system is reactive aluminosilicate glass and the acidic component of the system is organic polyacid containing functional groups such as —COOH, —SO3H, and —PO3H2. The glass ionomer mixture may also contain small amounts of low molecular weight complexing agent such as L- or D-tartaric acid for adjusting the kinetics of the cement setting process. In some embodiments, the glass-ionomer cements should be pretreated to make the surface of the polyacid powder less hydrophilic and therefore less susceptible to clumping due to moisture absorption. A preferable pretreatment includes the addition of some anti-caking hydrophobic agent to the dry cement mix. The agent could include some stearate salts (e.g., Mg, Ca, and Zn) or lecithin.
The acrylate component can include, but is not limited to, mono-functional acrylates, di-functional acrylates, tri-functional acrylates, tetra-functional acrylates, and combinations thereof. In addition, the acrylate can include, but is not limited to, water-soluble mono-, di-, and polymethacrylates with a low viscosity. In particular, the acrylate component can include, but is not limited to, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol monomethacrylates (e.g. molecular weight of about 400), ethylene glycol methacrylate, glycerine monomethacrylate, methyl methacrylate, 2-tert-butylaminomethyl methacrylate, tetrahydrofurfuryl methacrylate, ethyltriglycol monomethacrylate, dimethylaminoethyl methyacrylate, methacrylic acid, polyethylene glycol dimethacrylates (e.g., molecular weight of about 400), glycerine dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, urethane methacrylate, bis-EMA (e.g., ethoxylated bisphenol-A-dimethacrylate) as well as polymethacrylates (e.g., homo- and copolymers) of the stated mono- and dimethacrylates.
The acrylate component can also include, but is not limited to, metal salts of methacrylate and acrylate. In particular, the acrylate component can include, but is not limited to, sodium methacrylate, potassium methacrylate, ammonium methacrylate, magnesium methacrylate, calcium methacrylate, aluminum methacrylate, zinc methacrylate, zirconium methacrylate, zirconium trihydroxymonomethacrylate, zirconium dihydroxydimethacrylate, sodium acrylate, potassium acrylate, ammonium acrylate, magnesium acrylate, calcium acrylate, aluminum acrylate, zinc acrylate, zirconium acrylate, zirconium trihydroxymonoacrylate, and zirconium dihydroxyacrylate.
In addition, the acrylate component can also include, but is not limited to, acrylates having ethylenically unsaturated groups and acid groups (e.g., —COOH) or ethylenically unsaturated groups, acid groups (e.g., —COOH) and base groups (e.g., —NH2) in one component. The acrylates having ethylenically unsaturated groups also include the acid esters that can be formed from the above-stated mono- and dimethacrylates. The composition can include the acrylate component from 5% to about 50% and from about 20% to about 50% by weight of the composition.
The reducing agent can include chemicals such as, but not limited to, a water-soluble amine, metal salts, hydrazines, and combinations thereof. In particular, the reducing agent-can include chemicals such as, but not limited to, dimethyl-p-toluidine, dihydroxyethyl-p-toluidine and N,N-dimethylaminobenzoate, and combinations thereof. The composition can include the reducing agent from 0.1% to about 10% and from about 1% to about 5% by weight of the composition.
The oxidizing agent can include chemicals such as, but not limited to, persulphates, benzoyl peroxides, hydroperoxides, cobalt (III) and iron (III) salts, and hydrogen peroxides, and combinations thereof. In particular, the oxidizing agent can include chemicals such as, but not limited to, benzoyl peroxides. The composition can include the oxidizing agent from 0.1% to about 10% and from about 1% to about 5% by weight of the composition.
The light sensitive initiator can include, but is not limited to, UV initiators and/or visible initiators. The UV initiator can include chemicals such as, but not limited to, a free radical initiator, a cationic initiator, or combinations thereof. The free-radical initiator includes compounds that produce a free radical on exposure to UV radiation. The free-radical is capable of initiating a polymerization reaction. Exemplar free-radical initiators include, but are not limited to, benzophenones (e.g., benzophenone, methyl benzophenone, Michler's ketone, and xanthones), acylphosphine oxide type free radical initiators (e.g., 2,4,6-trimethylbenzoyldiphenyl phosphine oxide (TMPO), 2,4,6-trimethylbenzoylethoxyphenyl phosphine oxide (TEPO), and bisacylphosphine oxides (BAPO's)), azo compounds (e.g., AlBN), benzoins, and bezoin alkyl ethers (e.g., benzoin, benzoin methyl ether and benzoin isopropyl ether).
The free-radical initiator can be used alone or in combination with a co-initiator. Co-initiators are used with initiators that need a second molecule to produce a radical that is active in UV-systems. For example, benzophenone uses a second molecule, such as an amine, to produce a reactive radical. A preferred class of co-initiators are alkanolamines such as, but not limited to, triethylamine, methyldiethanolamine and triethanolamine
Suitable cationic initiators include, but are not limited to, compounds that form aprotic acids or Bronsted acids upon exposure to UV light sufficient to initiate polymerization. The cationic initiator used may be a single compound, a mixture of two or more active compounds, or a combination of two or more different compounds (e.g., co-initiators). Exemplary cationic initiators include, but are not limited to, aryldiazonium salts, diaryliodonium salts, triarylsulphonium salts, and triarylselenium salts.
The visible radiation initiator can include, but is not limited to, diketones (e.g., camphorquinone, 1,2-acenaphthylenedione, 1H-indole-2,3-dione, 5H-dibenzo[a,d]cycloheptene-10, and 11-dione), phenoxazine dyes (e.g., Resazurin, Resorufin), acylphosphine oxides, (e.g., diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide), and the like.
The composition can include the light sensitive initiator from 0.01% to about 5% and from about 0.01% to about 3% by weight of the composition.
The binder functions to, at least, as a solvent. In addition, the binder functions to stimulate a crosslinking reaction between the basic component and the acidic component. Furthermore, binder is capable of stimulating polymerization reaction between the acrylate component, the radical initiator, and the oxidizing agent. The binder can be a polar binder or a non-polar binder. The polar binder can include, but is not limited to, water, ethanol, hexanediol, pentanediol, water-soluble acryates and combinations thereof. The non-polar binder can include, but is not limited to, silanes, dimethylsilicone, chlorinated organic solvents (such as chloroform, carbon tetrachloride, o-dichlorobenzene), aliphatic alcohols, cyclohexane, dimethylaniline, triethylamine, 1,4-cyclohexadiene, and combinations thereof.
As mentioned above, the powder and/or the binder can include additional components such as, but not limited to, retardants, inhibitors, wetting agents, viscosity modifiers, surface tension modifiers, colorants (e.g., dyes, pigments, inks), dispersants, antioxidants, water retaining additives, accelerators, humectants, solvents, and combinations thereof.
Additional components can be used in the powder and/or the binder to obtain the proper balance of cure rate, layer-to-layer adhesion, toughness, and glass transition temperature, of the three-dimensional object. Furthermore, the components can be used to alter the physical and/or chemical properties (e.g., viscosity, reactivity, surface tension, bubble formation, and wetting of the ejection chamber) of the powder and/or the binder prior to and/or after being dispensed.
The retardant functions to, at least, slow down the setting reaction of the polyacid and the crosslinking multivalent cations. The retardant can include, but is not limited to, sodium phosphate, potassium phosphate, potassium oxalate, sodium oxalate, sodium carbonate, potassium carbonate, salicylic acid, tartaric acid, dihydroxytartaric acid, oxalic acid, citric acid, ethylenediamine tetraacetic acid (EDTA) and their sodium and potassium salts, sodium phosphate, sodium dihydrogen phosphate as well as sodium hydrogen phosphate, magnesium oxide and tin fluoride and combinations thereof. The composition can include the retardant from 1% to about 10% and from about 2% to about 8% by weight of the composition.
The inhibitor functions to, at least, quench premature curing reactions. The inhibitor can include, but is not limited to, t-butylhydroxy toluene, methyl ethyl ketone, and combinations thereof. The composition can include the inhibitor from 0.01% to about 1% and from about 0.01% to about 0.1% by weight of the composition.
The accelerator functions to, at least, crosslink with the acid component and/or the acrylate component and enhances the physical property of the three-dimensional object. The accelerator can form compounds such as, but not limited to, Al3+ compounds (e.g., Al(NO3)3, Al2(PO4)3, and Al2(SO4)3) and Zn2+ compounds (e.g., ZnO, Zn(NO3)2, and Zn(SO4)). The composition can include the accelerator from 0.1% to about 10% and from about 1% to about 5% by weight of the composition.
The wetting agent functions to, at least, wet the resistor. The wetting agent can include, but is not limited to, tergitols, ethylene glycols, and fluorosurfactants, and combinations thereof. The composition can include the wetting agent from 0.01% to about 3% and from about 0.1% to about 1% by weight of the composition.
The viscosity modifier functions to, at least, increase or decrease the viscosity of the binder composition. The viscosity modifier can include, but is not limited to, ethanol, hexanediol, pentanediol, ethylene glycol diacetate, potassium aluminum sulphate, isopropanol, ethylene glycol monobutyl ether, diethylene monobutyl ether, dodecyldimethylammonium proposane sulphonate, glycerine triacetate, ethyl acetoacetate, polyvinyl pyrrolidone, polyethylene glycol, polyacrylic acid, sodium polyacrylate, and combinations thereof. The composition can include the viscosity modifier from 1% to about 30% and from about 5% to about 20% by weight of the composition.
The surface tension modifier functions to, at least, increase or decrease the surface tension of the binder composition. In addition, the surface tension modifier functions to clear the inkjet orifice plate of extraneous liquid that might interfere with drop ejection. The surface tension modifier can include, but is not limited to, ethanol, hexanediol, pentanediol, tergitols, ethylene glycols, fluorosurfactants, and combinations thereof. The composition can include the surface tension modifier from 0.01% to about 30% and from about 0.1% to about 20% by weight of the composition.
The addition of fibers to the powder may be performed to vary and/or improve the mechanical properties (e.g., bending strength and fracture toughness) of the three-dimensional object. The fibers can include, but are not limited to, polymer fibers, ceramic fibers, natural fibers, carbon fibers, glass fibers, and combinations thereof. More specifically, the fibers can include, but are not limited to, cellulose fibers, wood fibers, polypropylene fibers, aramide fibers, silicon carbide fibers, aluminum silicate fibers, and derivative of each of these exemplary fibers. The powder can include fibers from 1% to about 30% and from about 3% to about 20% by weight of the composition.
The addition of filler functions to, at least, stiffen and smooth the surface of-the three-dimensional object. The fillers can include organic fillers and inorganic fillers. The organic fillers can include, but are not limited to, methacrylates (e.g., polymethylmethacrylate and polyhydroxyethylmethacrylate), polybutadiene styrene copolymers, maleic anhydride co-polymers, starch, starch derivatives, cellulose, cellulose derivatives, polycarbonates, polyepoxides, polyacrylates, polymethacryaltes, polyethylene and combinations thereof.
The inorganic fillers can include, but are not limited to, fumed silica, hydroxyapatite, layered double hydroxides, organic-inorganic clays ceramics, glasses, naturally occurring materials and their synthetic derivatives, polymer fillers, sand, quartz, silicon dioxide, aluminum oxide, titanium dioxide, aluminum hydroxide, nitrides (e.g. silicon nitride), kaolin, talc, wollstonite, feldspar, mica, zinc glass, boron silicate glass, and combinations thereof. The composition can include the filler from 1% to about 60% and from about 10% to about 50% by weight of the composition.
It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate,da concentration range of “about 0.1% to about 5%” should be interpreted to include not only the explicitly recited concentration of about 0.1 wt % to about 5 wt %, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%) within the indicated range.
Many variations and modifications may be made to the above-described embodiments. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.

Claims (19)

1. A composition, comprising:
a basic component;
an acidic component, wherein the acidic component is selected from alginic acid, gum arabic, nucleic acids, pectins, proteins, carboxymethylcellulose, ligninsulphonic acids, acid-modified starch, polyvinyl sulphonic acid, polystyrene sulphonic acid, polysulphuric acid, polyvinyl phosphonic acid, polyvinyl phosphoric acid, the homo- and copolymers of unsaturated aliphatic carbonic acids, the anhydrides of the unsaturated aliphatic carbonic acids, or combinations thereof;
at least one acrylate component;
oxidizing agent;
reducing agent;
a plurality of fibers, wherein the fibers are selected from polymer fibers, ceramic fibers, carbon fibers, glass fibers, or combinations thereof; and
a binder comprising a viscosity modifier and a surface tension modifier, the binder stimulating a reaction between the basic component and the acidic component, and wherein a polymerization reaction is initiated by the redox reaction between the oxidizing agent and the reducing agent.
2. The composition of claim 1, wherein the basic component is selected from metal oxides, metal oxide salts, reactive glasses, or combinations thereof.
3. The composition of claim 1 wherein at least one acrylate component is selected from mono-functional acrylates, di-functional acrylates, tri-functional acrylates, tetra-functional acrylates, or combinations thereof.
4. The composition of claim 1, wherein the oxidizing agent selected from persulphates, benzoyl peroxides, hydroperoxides, cobalt (III) salts, iron (III) salts, hydrogen peroxides, or combinations thereof.
5. The composition of claim 1, wherein the reducing agent is selected from water-soluble amines, metal salts, hydrazines, or combinations thereof.
6. The composition of claim 1, wherein the viscosity modifier is selected from ethanol, hexanediol, pentanediol, ethylene glycol diacetate, potassium aluminum sulphate, isopropanol, ethylene glycol monobutyl ether, diethylene monobutyl ether, dodecyldimethylammonium proposane sulphonate, glycerine triacetate, ethyl acetoacetate, polyvinyl pyrrolidone, polyethylene glycol, polyacrylic acid, sodium polyacrylate, or combinations thereof.
7. The composition of claim 1, wherein the surface tension modifier is selected from ethanol, hexanediol, pentanediol, tergitols, ethylene glycols, fluorosurfactants, or combinations thereof.
8. The composition of claim 1, wherein the basic component is from about 20% to 90% by weight of the solid freeform composition, the acidic component is from about 1% to 40% by weight of the solid freeform composition, the at least one acrylate component is from about 5% to 50% by weight of the solid freeform composition, the oxidizing agent is from about 0.1% to 10% by weight of the solid freeform composition, the reducing agent is from about 0.1% to 10% by weight of the solid freeform composition, the viscosity modifier is from about 1% to about 30% by weight of the solid freeform composition, and the surface tension modifier is from about 0.01% to about 30% by weight of the solid freeform composition.
9. The composition of claim 1, wherein a powder includes the basic component, the acidic component, a polyacrylate component, the fibers, and the oxidizing agent; and wherein the polar binder includes a polar solvent, an acrylate component, the surface tension modifier, the viscosity modifier, or the reducing agent.
10. The composition of claim 1, wherein a powder includes the basic component, a polyacrylate component, the fibers, and the oxidizing agent; and wherein the polar binder includes a polar solvent, the acidic component, an acrylate component, the surface tension modifier, the viscosity modifier, and the reducing agent.
11. The composition of claim 1, wherein a powder includes the basic component, a first acidic component, a polyacrylate component, the fibers, and the oxidizing agent; and wherein the polar binder includes a polar solvent, a second acidic component, an acrylate component, the surface tension modifier, the viscosity modifier, and the reducing agent.
12. The composition of claim 1, further comprising components selected from a retardant, an inhibitor, a wetting agent, a colorant, an organic filler, an inorganic filler, or combinations thereof.
13. The composition of claim 12, wherein the organic filler is selected from polymethylmethacrylate, polyhydroxyethylmethacrylate, or combinations thereof.
14. The composition of claim 1, further comprising:
a light sensitive radical initiator, wherein a polymerization reaction between the at least one acrylate component and the light sensitive initiator occurs upon exposure to light energy.
15. The composition of claim 14, wherein the light sensitive initiator is selected from ultraviolet initiators, visible initiators, or combinations thereof.
16. The composition of claim 14, wherein the basic component is from about 20% to 90% by weight of the solid freeform composition, the acidic component is from about 1% to 40% by weight of the solid freeform composition, the at least one acrylate component is from about 5% to 50% by weight of the solid freeform composition, the oxidizing agent is from about 0.1% to 10% by weight of the solid freeform composition, the reducing agent is from about 0.1% to 10% by weight of the solid freeform composition, and the light sensitive initiator is from about 0.01% to 5% by weight of the solid freeform composition.
17. The composition of claim 1, wherein the viscosity modifier is selected from ethanol, hexanediol, pentanediol, potassium aluminum sulphate, isopropanol, diethylene monobutyl ether, dodecyldimethylammonium proposane sulphonate, ethyl acetoacetate, polyvinyl pyrrolidone, sodium polyacrylate, or combinations thereof.
18. The composition of claim 1, wherein the surface tension modifier is selected from ethanol, hexanediol, pentanediol, tergitols, fluorosurfactants, or combinations thereof.
19. A composition, comprising:
a basic component;
an acidic component;
at least one acrylate component;
oxidizing agent;
reducing agent;
a plurality of fibers, wherein the fibers are selected from polymer fibers, ceramic fibers, carbon fibers, glass fibers, or combinations thereof; and a binder comprising a viscosity modifier and a surface tension modifier, the binder stimulating a reaction between the basic component and the acidic component, and wherein a polymerization reaction is initiated by the redox reaction between the oxidizing agent or the reducing agent,
wherein the basic component is a reactive glass; wherein the acidic component is a polyacrylic acid; wherein the acrylate is a difunctional acrylate; wherein the oxidizing agent is peroxide; wherein the reducing agent water-soluble amine; wherein the binder is water; wherein the viscosity modifier is ethanol; and wherein the surface tension modifier is a fluoro surfactant.
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